Catalytic de-halogenation of alkyl halides by copper surfaces

Oday H. Ahmed, Mohammednoor Altarawneh, Mohammad Al-Harahsheh, Zhong Tao Jiang, Bogdan Z. Dlugogorski

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The interplay of halogenated compounds with metal surfaces has been the focus of many experimental and theoretical studies. These investigations have mainly aimed to illustrate the potential dual role of transition metals and their oxides in mediating formation of toxic halogenated aromatics as well as their catalytic-assisted decomposition over these surfaces. An initial and prominent step in conversion of these precursors into heavier halogenated aromatics signifies their dissociative adsorption on metallic species readily present in the combustion media. This contribution represents a systematic computational study to examine thermo-kinetic parameters underlying rupture of Cl/Br-C bonds in halogenated model compounds (namely; 2-chloropropane, chloromethane, chloroethyne, chloropropene, chlorobenzene, 2-bromopropane, bromomethane, bromoethyne, bromopropene, and bromobenzene) over the Cu(100) surface. These compounds adapt very weak physisorbed molecular states evidenced by marginal adsorption energies and minimal structural changes, in reference to their gas phase molecules. The calculated reaction barriers for Cl/Br-C bond fissions are scattered in the range of 8.3-37.2 kcal mol -1 . Stronger Cl-C bonds in reference to Br-C bonds (in the gas phase) translate into higher corresponding reaction barriers for the former. The calculated reaction rate constants and activation energies reveal faster rate for the decomposition of the brominated species. Our calculations of the activation energies correlate very well with analogues experiment values.

Original languageEnglish
Pages (from-to)7214-7224
Number of pages11
JournalJournal of Environmental Chemical Engineering
Volume6
Issue number6
DOIs
Publication statusPublished - Dec 2018
Externally publishedYes

Fingerprint

Halogenation
halide
Copper
methyl bromide
2-bromopropane
copper
activation energy
Activation energy
Gases
Methyl Chloride
decomposition
Decomposition
adsorption
Adsorption
chlorobenzene
Poisons
transition element
theoretical study
Kinetic parameters
gas

Cite this

Ahmed, O. H., Altarawneh, M., Al-Harahsheh, M., Jiang, Z. T., & Dlugogorski, B. Z. (2018). Catalytic de-halogenation of alkyl halides by copper surfaces. Journal of Environmental Chemical Engineering, 6(6), 7214-7224. https://doi.org/10.1016/j.jece.2018.11.014
Ahmed, Oday H. ; Altarawneh, Mohammednoor ; Al-Harahsheh, Mohammad ; Jiang, Zhong Tao ; Dlugogorski, Bogdan Z. / Catalytic de-halogenation of alkyl halides by copper surfaces. In: Journal of Environmental Chemical Engineering. 2018 ; Vol. 6, No. 6. pp. 7214-7224.
@article{7a9e1c622c204062bae835693220f6fe,
title = "Catalytic de-halogenation of alkyl halides by copper surfaces",
abstract = "The interplay of halogenated compounds with metal surfaces has been the focus of many experimental and theoretical studies. These investigations have mainly aimed to illustrate the potential dual role of transition metals and their oxides in mediating formation of toxic halogenated aromatics as well as their catalytic-assisted decomposition over these surfaces. An initial and prominent step in conversion of these precursors into heavier halogenated aromatics signifies their dissociative adsorption on metallic species readily present in the combustion media. This contribution represents a systematic computational study to examine thermo-kinetic parameters underlying rupture of Cl/Br-C bonds in halogenated model compounds (namely; 2-chloropropane, chloromethane, chloroethyne, chloropropene, chlorobenzene, 2-bromopropane, bromomethane, bromoethyne, bromopropene, and bromobenzene) over the Cu(100) surface. These compounds adapt very weak physisorbed molecular states evidenced by marginal adsorption energies and minimal structural changes, in reference to their gas phase molecules. The calculated reaction barriers for Cl/Br-C bond fissions are scattered in the range of 8.3-37.2 kcal mol -1 . Stronger Cl-C bonds in reference to Br-C bonds (in the gas phase) translate into higher corresponding reaction barriers for the former. The calculated reaction rate constants and activation energies reveal faster rate for the decomposition of the brominated species. Our calculations of the activation energies correlate very well with analogues experiment values.",
keywords = "Copper, DFT, Halogenated hydrocarbons, Reaction mechanisms",
author = "Ahmed, {Oday H.} and Mohammednoor Altarawneh and Mohammad Al-Harahsheh and Jiang, {Zhong Tao} and Dlugogorski, {Bogdan Z.}",
year = "2018",
month = "12",
doi = "10.1016/j.jece.2018.11.014",
language = "English",
volume = "6",
pages = "7214--7224",
journal = "Journal of Environmental Chemical Engineering",
issn = "2213-3437",
publisher = "Elsevier",
number = "6",

}

Ahmed, OH, Altarawneh, M, Al-Harahsheh, M, Jiang, ZT & Dlugogorski, BZ 2018, 'Catalytic de-halogenation of alkyl halides by copper surfaces', Journal of Environmental Chemical Engineering, vol. 6, no. 6, pp. 7214-7224. https://doi.org/10.1016/j.jece.2018.11.014

Catalytic de-halogenation of alkyl halides by copper surfaces. / Ahmed, Oday H.; Altarawneh, Mohammednoor; Al-Harahsheh, Mohammad; Jiang, Zhong Tao; Dlugogorski, Bogdan Z.

In: Journal of Environmental Chemical Engineering, Vol. 6, No. 6, 12.2018, p. 7214-7224.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Catalytic de-halogenation of alkyl halides by copper surfaces

AU - Ahmed, Oday H.

AU - Altarawneh, Mohammednoor

AU - Al-Harahsheh, Mohammad

AU - Jiang, Zhong Tao

AU - Dlugogorski, Bogdan Z.

PY - 2018/12

Y1 - 2018/12

N2 - The interplay of halogenated compounds with metal surfaces has been the focus of many experimental and theoretical studies. These investigations have mainly aimed to illustrate the potential dual role of transition metals and their oxides in mediating formation of toxic halogenated aromatics as well as their catalytic-assisted decomposition over these surfaces. An initial and prominent step in conversion of these precursors into heavier halogenated aromatics signifies their dissociative adsorption on metallic species readily present in the combustion media. This contribution represents a systematic computational study to examine thermo-kinetic parameters underlying rupture of Cl/Br-C bonds in halogenated model compounds (namely; 2-chloropropane, chloromethane, chloroethyne, chloropropene, chlorobenzene, 2-bromopropane, bromomethane, bromoethyne, bromopropene, and bromobenzene) over the Cu(100) surface. These compounds adapt very weak physisorbed molecular states evidenced by marginal adsorption energies and minimal structural changes, in reference to their gas phase molecules. The calculated reaction barriers for Cl/Br-C bond fissions are scattered in the range of 8.3-37.2 kcal mol -1 . Stronger Cl-C bonds in reference to Br-C bonds (in the gas phase) translate into higher corresponding reaction barriers for the former. The calculated reaction rate constants and activation energies reveal faster rate for the decomposition of the brominated species. Our calculations of the activation energies correlate very well with analogues experiment values.

AB - The interplay of halogenated compounds with metal surfaces has been the focus of many experimental and theoretical studies. These investigations have mainly aimed to illustrate the potential dual role of transition metals and their oxides in mediating formation of toxic halogenated aromatics as well as their catalytic-assisted decomposition over these surfaces. An initial and prominent step in conversion of these precursors into heavier halogenated aromatics signifies their dissociative adsorption on metallic species readily present in the combustion media. This contribution represents a systematic computational study to examine thermo-kinetic parameters underlying rupture of Cl/Br-C bonds in halogenated model compounds (namely; 2-chloropropane, chloromethane, chloroethyne, chloropropene, chlorobenzene, 2-bromopropane, bromomethane, bromoethyne, bromopropene, and bromobenzene) over the Cu(100) surface. These compounds adapt very weak physisorbed molecular states evidenced by marginal adsorption energies and minimal structural changes, in reference to their gas phase molecules. The calculated reaction barriers for Cl/Br-C bond fissions are scattered in the range of 8.3-37.2 kcal mol -1 . Stronger Cl-C bonds in reference to Br-C bonds (in the gas phase) translate into higher corresponding reaction barriers for the former. The calculated reaction rate constants and activation energies reveal faster rate for the decomposition of the brominated species. Our calculations of the activation energies correlate very well with analogues experiment values.

KW - Copper

KW - DFT

KW - Halogenated hydrocarbons

KW - Reaction mechanisms

UR - http://www.scopus.com/inward/record.url?scp=85056842757&partnerID=8YFLogxK

U2 - 10.1016/j.jece.2018.11.014

DO - 10.1016/j.jece.2018.11.014

M3 - Article

VL - 6

SP - 7214

EP - 7224

JO - Journal of Environmental Chemical Engineering

JF - Journal of Environmental Chemical Engineering

SN - 2213-3437

IS - 6

ER -